Anti-reflection coating with transparent surface conductive layer

ABSTRACT

An anti-reflection coating layer system is composed of 4 oxide layer and more specifically the material of surface layer is a transparent conductive coating and has a high refractive index between 1.9 to 2.1. The materials of surface layer are a kind of transparent conductive coating such as SnO 2 , ZnO 2 , In 2 O 3  and ITO. Because of the surface layer has a good electrical conductive property, the layer system reduce much of work of grounding process and also increase the total yield in the volume production.

FIELD OF THE INVENTION

[0001] The present invention is related to an optically effective layer system used for plastic and/or glass substrate, whereby the layer system has a high anti-reflection effect. More specifically the invention related to a layer structure, which contains a transparent conductive oxide as surface layer and has a photopic reflectance below 0.5%.

BACKGROUND OF THE INVENTION

[0002] U.S. Pat. No. 4,921,760, whose disclosure is a multi-layer anti-reflection coating with excellent adhesion between CeO₂ layer and synthetic resin. The layer system including CeO₂, Al₂O₃, ZrO₂, SiO₂, TiO₂ and Ta₂O₅. All the thin films of the layer system are oxide materials. There are 3 to 5 thin layers in the layer system. For a given example, the total thickness of the 5 layer structure was about 3580 Angstroms. The material of the surface layer of the layer system is SiO₂ which has a low-refractive index about 1.46 at 550nm.

[0003] U.S. Pat. No. 5,105,310, whose disclosure is a multi-layer anti-reflection coating designed for deposition in in-line coating maching by reactive sputtering. The layer system including TiO₂, SiO₂, ZnO, ZrO₂ and Ta₂O₅. All the thin films of the layer system are oxide material. There are 4 to 6 thin layers in the layer system. For a given example, the total thickness of the 6-layer structure was about 4700 Angstroms. The material of the surface layer of the layer system is SiO₂, which has a low-refractive index about 1.46 at 550nm.

[0004] U.S. Pat. No. 5,091,244 and 5,407,733 disclosed a new type electric conductive light-attenuating anti-reflection coating. The major claim is an article comprising of nitrides of certain transition metal to provided an electrically-conductive, light-attenuating, anti-reflection surfaces. The layer systems including TiN, NbN, SnO₂, SiO₂, Al₂O₃, and Nb₂O₅. The thin films of the layer system are nitride and oxide materials. There are 3 to 4 thin layers in the layer system. For a given example, the total thickness of the 4 layer structure was about 1610 Angstroms. The transmission of visible light of these two layer systems is below 50%. The material of the surface layer of the layer system is SiO₂ which has a low-refractive index about 1.46 at 550 nm.

[0005] U.S. Pat. No. 5,147,125, whose disclosure is a multi-layer, anti-reflection coating using zinc oxide to provide UV rejection for wave-lengths shorter than 380 nm. The layer system including TiO₂, SiO₂, ZnO, and MgF₂. All the thin films of the layer system are oxide and floride. There are 4 to 6 thin layers in the layer system. For a given example, the total thickness of the 5 layer structure was about. 7350 Angstroms. The material of the surface layer of the layer system is MgF₂ which has a low-refractive index about 1.38 at 550 nm.

[0006] U.S. Pat. No. 5,170,291 disclose a 4 layer system which is optical effective and has a high anti-reflective effect. The layers can be formed by either a pyrolytic method, a plasma-supported chemical vapor deposition method, a sputtering method or a chemical deposition method. The layer system including SiO₂, TiO₂, Al₂O₃, ZnS, MgO and Bi₂O₃. For a given sample, the total thickness of the 4 layer structure was about 2480 Angstroms. The material of the surface layer of the layer system is SiO₂ which has a low-refractive index about 1.46 at 550 nm.

[0007] U.S. Pat. No. 5,216,542 whose disclosure is a 5 layer coating with high anti-reflection effect. The process use an adhesive layer of Ni, Cr or NiCr metal with a thickness about 1 nm (manometer). Other four layers are compose of SnO₂, ZrO₂, ZnO, Ta₂O₅, NiO, CrO₂, TiO₂, Sb₂O₃, In₂O₃, Al₂O₃, SiO₂, TiN and ZrN. For a given example, the total thickness of the 5 layer structure was about 2337 Angstroms. The transmission of visible light of this layer system is below 30%. The material of the surface layer of the layer system is SiO₂ which has a low-refractive index about 1.46 at 550 nm.

[0008] U.S. Pat. No. 5,541,770 whose disclosure is a light attenuating anti-reflection coating including electrically conductive layers. It is a four or five layer system. A light absorption high refractive index metal such as Cr, Mo and W was used as a optically effective thin film in the layer system. The other three or four layers are TiO₂, ITO, Al₂O₃, SiO₂ and TiN. The patent shows that the majority materials of the layer system are oxide and nitride, only one metal film was used as an optical effective thin film in the anti-reflection coating. For a given example, the total thickness of the 5 layer structure was about 1495 Angstroms. The transmission of visible light of this layer system is below 60%. The material of the surface layer of the layer system is SiO₂ which has a low-refractive index about 1.46 at 550 nm.

[0009] U.S. Pat. No. 5,362,552 whose disclosure is a 6-layer anti-reflection coating includes three layers of electrically- conductive metal oxide. The layer system including SiO₂, ITO, Nb₂O₅, and Ta₂O₅. Up to a total optical thickness of about one-wavelength of visible light of the electrically conductive metal oxide may be included in the coating. For one of given example of 6 layer structure, the materials and thickness of the majors two layers within this 6 layer system are SiO₂, 854 Angstroms and ITO 1975 Angstroms. Anyway, The material of the surface layer of the layer system is SiO₂ which has a low-refractive index about 1.46 at 550 nm.

[0010] U.S. Pat. No. 5,579,162 whose disclose is a 4-layer anti-reflection coating for a temperature sensitive substrate such as plastic. One layer is a DC reactively sputtered metal oxide which may be deposited quickly and without imparting a large amount of heat to the substrate. The layer system including SnO₂, SiO₂ and ITO. For one of given example of the 4 layer structure, the materials and thickness of the majority two layers within this system are SnO₂, 763 Angstroms and SiO₂ 940 Angstroms. The material of the surface layer of the layer system is SiO₂ which has a low-refractive index about 1.46 at 550 nm.

[0011] U.S. Pat. No. 5,728,456 and 5,783,049, disclosed An improved way to deposit anti-reflection coating on plastic film. The multi-layer thin films was coated by a roller coating with sputtering process. The layer system including ITO, SiO₂ and a thin lubricating over layer which is a solvent-soluble fluoropolymer. For a given example, the total thickness of the 6 layer system was about 2630 Angstrom. The material of the surface layer of the layer system is SiO₂ which has a low-refractive index about 1.46 at 550 nm.

[0012] The above description show clearly that the material of surface thin layer of the conventional optical layer system is SiO₂ or MgF₂, which has a low refractive index of 1.46 and 1.38 at 5 50 mm, respectively.

SUMMARY OF THE INVENTION

[0013] An object of the present invention is to provide an anti-reflection coating layer system composed of 4 oxide layer and more specifically the material of surface layer is a transparent conductive coating and has a high refractive index between 1.9 to 2.1.

[0014] The process of manufacturing oxide thin film in volume production was high reliable and was routinely used in the industries such as semiconductor, disc head, LCD, CRT, architechture glass, touch sensor, screen filter and plastic web coating for a several ten years.

[0015] It is well known that conventional layer structure for an anti-reflection optical coating has a general principle. The basic principle is that the surface layer of the optical coating is a material of low refractive index such as SiO₂ with refractive index of 1.46 or MgF₂with refractive index 1.38. However, when we applied the anti-reflection coating on the display industry for example screen filter for computer monitor, or low reflection glass for flat CRT, there are some bottleneck in the process of high volume mass production. The basic reason is in the convention optical layer structure the conductive layer was buried by an insulating layer for example SiO₂ or MgF₂.

[0016] In the general design rule of an anti-reflection coating, the first layer deposited on a substrate surface is a material with high refractive index (namely H), and follow by a second layer which is a material of low refractive index (namely L). The basic design rule for the conventional anti-reflection coating has a layer structure such as HLHL or HL HL HL. In a simple case if the materials of H is ITO and the materials of L is SiO₂, the 4 layer structure is Glass/ITO/SiO₂/ITO/SiO₂. Because of ITO is a transparent conductive material, the multi-layer coating of this layer structure has electrical conductivity below 1000 Ω/□, and can be used as EMI shielding and/or electric static discharge when conductive coating layer was bonded to ground. However, trouble phenomena are the surface material of the convention layer structure is SiO₂ and the typical thickness of SiO₂ layer is about 1000 Å. The material characteristic of SiO₂ is high density, inert property in chemical and is a very good insulating layer for electric. In the process of application of conventional anti-reflection coating on the display industry, it is hard work to make an electrical contact with the buried ITO layer which was isolated by outermost SiO₂ layer. For a typical grounding process to make a metal contact with ITO layer, it needs a ultra-sonic welding procedure to break the insulating layer (SiO₂) and to make sure good contact of tin solder with the buried ITO conductive layer. This process is a bottleneck for the application of anti-reflection coating in high volume.

[0017] On the other hand, the ultra-sonic welding process will produce small and bright contamination from tin spot because of the liquid tin, and explosive energy of ultra-sonic. This process also produces non-consist contact resistance for each bus bar line. It is because of the ultrasonic-welding process can not guarantee to break the insulating coating at the same depth evenly and to get a uniform contact resistance with ITO layer.

[0018] The drawbacks mention above will reduce the yield of the manufacturing process for the application of conventional anti-reflection coating. Therefore, It is quiet important to have an anti-reflection coating by using ITO conductive film as a material of surface layer. However, it is unusual in the design principle of optical layer structure. As mention above, the conventional design principle for a 4 layer anti-reflection coating is HLHL. However, the layer structure we provided is HHLH which is quiet different from conventional design of anti-reflection coating. The present invention is to provide an anti-reflection layer system compose of 4 layers of oxide materials and the materials of the surface layer has a high-refractive index between 1.9 to 2.1. The materials of surface layer are a kind of transparent conductive coating such as SnO₂, ZnO₂, In₂O₃ and ITO. Because of the surface layer has a good electrical conductive property, the layer system reduce much of work of grounding process and also increase the total yield in the volume production. The present invention provided a surface conductive layer structure of anti-reflection coating, which can be applied not only on display industry but also on touch sensor industry for glass and plastic substrate.

[0019] There are four layers, namely, the first, second, third and fourth layers in consecutive numerical order beginning with the layer furthest from the substrate for the present invention of anti-reflection coating. The each layer was described in terms of physical thickness or optical thickness. The optical thickness is a mathematical product of a layers thickness and its refractive index. It is described as a fraction of a designed wavelength. In the present invention the designed wavelength is about 520 nm.

[0020] The first or the surface layer is a transparent conductive oxide material. The oxide layer, preferably ITO substantially slightly absorption for visible light, has a refractive index between 1.9 to 2.1 at a wavelength of about 520 nanometer (nm) and a physical thickness between 10 nm to 40 nm at the design wavelength.

[0021] The second layer is an oxide material. The oxide layer preferably SiO₂, substantially non-absorption for visible light, has a refractive index between 1.45 to 1.50, at a wavelength of about 520 nm and a physical thickness between 30 to 60 nm at the design wavelength.

[0022] The third layer is an oxide material. The oxide layer, preferably NbO, substantially non-absorption for visible light, has a refractive index between 2.1 to 2.3 at a wavelength of about 520 nanometer (nm) and an physical thickness between 30 nm to 80 nm at the design wavelength.

[0023] The fourth or the innermost layer is an oxide material. The oxide layer, preferably NbSiO substantially non-absorption for visible light, has a refractive index between 1.9 and 2.1 at a wavelength of about 520 nm and a physical thickness between 40 to 80 nm at the design wavelength.

[0024] In the preferred embodiment, the 4 layers coating include a first layer of ITO having a thickness about 15 nm, a second layer of SiO₂ having a thickness about 58 nm, a third layer of NbO having a thickness about 45 nm and a fourth layer of NbSiO having a thickness about 67 nm.

[0025] The stated objects are achieved by the invention, a conductive front surface with a resistance between 10² Ω/square˜10³ Ω/square can be obtained from the ITO coating, and a smooth wide band reflection spectrum can be obtained on the glass or plastic substrate in the visible range from 400 nm to 700 nm. It is easy demonstrated that the process is simple, reliable, easy control and economically. It has become possible in this way to produce an anti-reflection coating with a good surface conductivity. Of particulate advantage, an in-line sputtering system was suggest to deposit the layer system of the present invention for low cost and high volume manufacturing.

[0026] On the other hand, the layer system of this invention is of high conductive for EMI (Electromagnetic Interference) shielding, high transparent for touch sensing, low reflection for optical view, high scratch resistance for surface hardness, and low cost for manufacturing. For instance, the layer system has a surface resistance between 10² Ω/square to 10³ Ω/square and is hard enough to pass the scratch test of military standard MIL-C-48497.

[0027] Thereby, a DC or AC magnetron sputtering can be provided to deposit the first layer from a ITO target in the presence of a sputter gas of Ar and a very small partial pressure of O₂, under a given total pressure of approximately 3 m Torr (m=mili=0.001), For the second layers, it is proposed that by using AC magnetron sputter from the silicon target, a layer of SiO₂ is generated in the presence of a sputter gas mixture comprising Ar and O₂, under a given pressure of 2 m Torr. For the third layers, it is proposed that via AC or pulse DC reactive sputtering from the Nb target, a layer of Nb₂O₅ is generated in the presence of a sputter gas mixture comprising Ar and O₂, under a given pressure of approximately 2.5 m Torr. For the fourth layer, it is proposed that via AC reactive sputtering from the NbSi target, a layer of NbSiO_(4.5) is generated in the presence of a sputter gas mixture comprising Ar and O₂, under a given pressure of approximately 2 m Torr.

[0028] The following advantages are achieved with the invention. The problem of transparent conductive ITO layer, which was isolated by an insulating SiO2 film in a conventional anti-reflection layer system, is solved. The present invention provided a four-layer system in which the surface material is ITO and has a refractive index between 1.9 and 2.1.

[0029] Because of the surface layer of the anti-reflection coating is electrical conductive, several simple process can be applied to make a good electrical contact with the anti-reflection coating easily. An example is to use this layer system in a touch sensor.

[0030] On the application of screen filter or flat-CRT, the conventional grounding method by using ultra-sonic welding process that produces small and bright contamination of tin spot will be replaced. The process of final assembling of anti-reflection coating on screen filter or flat CRT will be simplified. The problem of formation non-uniform electric contact between the isolated conductive ITO layer and tin solder will be solved. The yield of the grounding process will increase. On the other hand, the layer structure also can be used as a basic coating of industry of touch sensor.

[0031] Accordingly, the present invention having a 4 layers system composed of an electrical conductive materials as a surface layer which is a simple easy, economic process for the anti-reflection coating on glass and plastic substrate.

BRIEF DESCRIPTION OF THE DRAWINGS

[0032]FIG. 1 schematically shows a cross sectional view of a layer system according to the present invention.

[0033]FIG. 2 shows the measured reflection curve in percent versus wavelength in nm of a layer system according to the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0034] The present invention related to an oxide based anti-reflection coating with 4 layers. The multiplayer structure are numbered in sequence beginning from the outermost layer i.e. the layer furthest from a substrate surface on which the thin films is deposited. Layers thickness values are specified as either a physical thickness in nm or as an optical thickness as some fraction or multiple of a wavelength of visible light. The typical value is 520 nm.

[0035] The layer structure of a preferred embodiment of the present invention is shown in FIG. 1. A substrate 6 can be composed of glass, a plastic foil or another see-through materials. A front surface of substrate, namely side 5, is that side of substrate facing the observer. The direction of viewing is indicated by arrow 7. A layer 4, which is contacting the front side 5 of the substrate 6, is called a fourth layer 4. In the direction to the observer follows the third layer 3 being arranged on the fourth layer 4, which is next to the front surface of the substrate. The second layer 2 being arranged on the third layer 3. The first layer or the outermost layer 1 being arranged on the second layer 2. The layers 1, 2, 3 and 4 form a layer system of the present invention.

[0036] The first layer, or the outermost layer 1 is ITO layer with a thickness of 15 nm. The ITO has a refraction index of about 1.9˜2.1 at a wavelength of about 520 nm. The second layer 2 of the layer system is a SiO₂ layer of a thickness about 58 nm. The second layer has a refractive index of about 1.46 at a wavelength of about 520 nm. The third layer is an NbO layer of a thickness of 45 nm. The NbO layer has a refractive index of about 2.2 at a wavelength of about 520nm. The fourth layer, or innermost layer 4 of the layer system is a NbSiO layer of a thickness about 67 nm. The fifth layer has a refractive index of about 1.8 at a wavelength of about 520 nm.

[0037]FIG. 2. Shows the real reflection spectrum for the layer system. The reflection was measured in percent at the front surface of the glass. The visible spectrum extends from a wavelength of 400 nm to a wavelength of 700 nm. The curve reveals clearly that the reflection in the core wavelength region of the visible light particularly between 460 and 600 nm is extra ordinarily low. It lies below 0.3%. This result was as good as the reflection spectrum measured from the layer system composed of the basic design of HLHL oxide materials.

[0038] Table 1 shows the detail data of reflection spectrum ranging from 400 nm to 700 nm. The sputtering of oxide layer 2, 3 and 4 were performed with a magnetron cathode by using an AC sputter method in a reactive gas atmosphere composed of a gas mixture of Ar and O₂. On the other hand, for first layer, namely ITO, the sputtering was performed with a magnetron cathode by using a DC or pulse DC sputter method in a reactive gas atmosphere composed of a gas mixture of Ar and very slightly amount of O₂. The target material for layer 4, 3, 2 and 1 were NbSi, Nb, Si and ITO respectively. The target to substrate distance was about 15 cm. A heating device was applied in sputtering system. The substrate temperature was kept at 100 to 300° C. during sputtering process. TABLE 1 Wavelength (nm) Reflection (percent) 400 8.10 420 2.80 440 0.63 460 0.10 480 0.08 500 0.10 520 0.10 540 0.08 560 0.06 580 0.10 600 0.26 620 0.80 640 1.80 660 2.80 680 4.20 700 5.40

[0039] The working pressure during sputtering was described as following:

[0040] Sputtering for the layer 4 : 2 m Torr

[0041] Sputtering for the layer 3 : 2.5 m Torr

[0042] Sputtering for the layer 2 : 2 m Torr

[0043] Sputtering for the layer 1 : 3 m Torr

[0044] Although various minor modification may be suggested by those versed in the art, it should be understood that we wish to embody within the scope of the patent granted hereon all such modifications as reasonably and properly come within the scope of our contribution to the art. 

We claim:
 1. An anti-reflection conducting coating comprising five layers designated the first, second, third, fourth and fifth layers in consecutive numerical order beginning with the layer farthest from the substrate; said first layer being arranged on the second layer and comprising a high refracting material of oxide, the layer having a physical thickness of 10˜40 nm; said second layer being arranged on the third layer and comprising a low refracting material of oxide, the layer having a physical thickness of 30˜60 nm; said third layer being arranged on the fourth layer and comprising a high refracting material of oxide, the layer having a physical thickness of 30˜80 nm; and said fourth layer being arranged on the front surface on the substrate and comprising a high refracting material of oxide, the fifth layer having a physical thickness of 40˜80 nm.
 2. The anti-reflection conductive coating of claim 1, where said substrate is plastic.
 3. The anti-reflection conductive coating of claim 1, where said substrate is glass.
 4. The anti-reflection conductive coating of claim 1, wherein the first layer is ITO, said second layers are of SiO₂, third layers is NbO and fourth layer is NbSiO.
 5. The anti-reflection conductive coating of claim 1, wherein the first layer comprises oxides selected from a group consisting of ITO, SnO₂, ZnO, In₂O₃, SnO₂: F, SnO₂: Sb, ZnO : Al, In₂O₃ : ZnO, SnO2: ZnO and In₂O₃ MgO.
 6. The anti-reflection conductive coating of claim 1, wherein the second layer comprises oxide selected from a group consisting of SiO2 and SiAlO₂.
 7. The anti-reflection conductive coating of claim 1, wherein the third layer comprises oxide selected from a group consisting of ITO, Ta₂O₅, NbO and TiO and a mixtures of these oxides.
 8. The anti-reflection conductive coating of claim 1, wherein the fourth layer comprises oxide selected from a group consisting of TaSiO, NbSiO, TiSiO, InSiO, SnSiO and a mixtures of these oxides.
 9. The anti-reflection conductive coating of claim 1, wherein the first layer is composed of a oxide material with a refractive index between 1.9 and 2.1; the second layer is composed of a oxide material with a refractive index between 1.46 and 1.5; the third layer is composed of a oxide material with a refractive index between 2.1 and 2.3; the fourth layer is composed of a oxide material with a refractive index between 1.90 and 2.1.
 10. The anti-reflection conductive coating of claim 1, wherein the those layers are formed by evaporation or sputtering process manufacturing in a batch or in-line vacuum system.
 11. The anti-reflection conductive coating of claim 1, wherein the layer structure can be used a basic coating industry of touch sensor. 